Dyestuffs of the anthraquinone oxazole series



Patented Sept. 26, 1939 DYESTUFFS OF THE ANTHRAQUIN NE OXAZOLESERIESGeorg Kriinzlein,

Frankfort-on-the-Main, and" Hans Schlichenmaier, Kelkheim in Taunus,

ermany, assignors to General Inc., New York, ware No Drawing.

5 Claims.

The present; invention relates to dyestuffs of the anthraquinone oxazoleseries whichtmay be after-chromed.

We have found that The ox azole is treated in' the heat, at temperaabout60 C. and about 160 C.,

quinone-1.2- (N) -aryl-oxa2oles. advantageously tures between added tothe reaction mixture. Compounds'are which dissolve easilyin water to aThedried dyestnifs brown powders. By dissolving them in Water andsaltingthem out, for instance,

dyestuifs are They dissolve in concentrated at yellowish-red solution.

according to the described method dyestuffs capable of beingafter-chromed may be obtained from aminoanthraquinone-oxazoles.

The following examples serve to illustrate the Aniline Works; j

., a corporation of Dela- Application August 2, 1935, Serial In GermanyAugust 25, 1934 invention but the reto;' the parts areby weight unlessstated 7 otherwise:

(1) 6 parts of 4-aminoanthraquinone-1.2-(N)- phenyloxazole of Itheformula;

ainable' acc'or (obt tionfSe'rial No," h 21 19 35 in the name ofGe'orgKranzlein, Hans Sohlichen- The ipro'du ct is poured" on about Anr'eddish brown precipitate separates which: increases with the coolingof" the dyeingof very good levelling-power :and, very good fastnessi.to. washing, to fulling and to light is obtained. 1 s

-(2) fi'parts of the above 'oxazole aretreated for 4-5 hours at 90-100?C.-:with 160 parts by 'vol-ume of turning sulfuric :acid containing 20 1per... cent:

fastness are obtained described in Example (3) 2 parts of the aboveainino-oxazole are dissol ed with 3 parts of crystallized boric acid inthey are not intended to limit it properties similar to those of theproducts obtainable according to Examples 1 and 2.

(4) 2 parts of 4-aminoanthraquinone-1:2-paratolyloxazole are warmed inthe presence of 3 parts of boric acid with 30 parts by volume of furicanhydride for one hour on the water bath. By working the product up asdescribed in Example 3, a dark brown powder is obtained, which dissolvesin water to an intensely bluish-violet color and dyes wool violet tints.

(5) By saponifying the anthraquinone-oxazole, obtainable from 1-hydroxy2.4-'diaminoanthraquinone and meta-chlorobenzoyl-chloride byboilsponding amine is obtained which when recrystallized fromalpha-chloronaphthalene. forms red, needle-shaped crystals melting at314 C. 40 parts of this amine are heated for 1 /2 hours at 150 C. in 15times their weight of fuming sulfuric acid containing 20' per cent ofsulfuric anhydride. The solution is then poured on a small quantity ofice, the violet precipitate is filtered with suction, dissolved again inhot water and the disulfonic acid of the dyestuff is precipitated in theform of its potassium salt.

When after-chromed on the fiber the dyestuff yields bluish-gray, evendyeings of very good fastness properties.

(6) The anthraquinone-oxazole,obtainable from1-hydroxy-2.4-diaminoanthraquinone and metamethoxy-benzoylchloride byboiling the components in nitrobenzene, is saponified with sulfuric acidand yields an amine which, when recrystallized from dichlorobenzenemelts at 325 C. This amine is heated for 1 /2 hours at C. to C. in 15times its weight of fuming sulfuric acid containing 20 per cent ofsulfuric anhydride and yields, when worked up as-described in thepreceding example, a dyestuff which, when after-chromed on the fiber,dyes wool a blue-gray tint of good tinctorial properties and very goodfastness to light.

(7) The anthraquinone-oxazole,obtainablefrom1-hydroxy-2.4-diaminoanthraquinone and orthochlorobenzoylchloride byboiling the components in nitrobenzene, is saponified with sulfuric acidand the thus obtained amine, melting at 308 0., is sulfonated for about1 hour at C. as de- The dyestuff which has been purified by way of thesodium salt dyes wool, when afterchromed on the fiber, grayish bluetints of the same good fastness properties as those of the dyestuffsobtainable according to the preceding examples.

We claim:

1. A compound of the group consisting of the compounds of the formula I\0\/ TS0dOE l NH:

It is then a light-brown powder, having tintorial fuming sulfuric acidcontaining 30 per cent. of suling the components in nitrobenzene, thecorrewherein aryl comprises radicals of the group consisting of phenyland phenyl substituted by noncyolic monovalent substituents and theposition of the hydroxyl and sulfo groups in the molecule is not known,and the alkali metal salts thereof.

2. A compound of the group consisting of the compounds of the formula ONH:

wherein X means a member of the group consisting of hydrogen, halogen,alkoxy and alkyl, and the position of thehydroxyl and sulfo groups inthe molecule is not known, and the alkali metal salts thereof.

3. A compound of the group consisting of the compound of the formulaSO1OH g NHr wherein the position of the hydroxyl and sulfo groups in themolecule is not known, and the sodium salt thereof,-forming ablack-brown powder which dyes wool violet tints which, on being treatedwith an agent yielding chromium, change to greenish-blue'tints of verygood leveling power and very good fastness to washing, to fulling and tolight.

4. A compound of the compound of the formula group consisting of the andthe sodium salt thereof, yielding on wool, when after-chromed on thefiber, bluish-gray even dyeings of very good fastness properties.

5. A compound of the group consisting of the and the sodium saltthereof, yielding on wool, when after-chromed on the fiber, a blue-graytint of good tinctorial properties and very good fastness properties.

GEORG KRANZLEIN.

HANS SCHLICHENMAIER.

